Letter

pubs.acs.org/JPCL

Intermolecular Interactions in Highly Disordered, Confined Dense N2

Mario Santoro,*,†,‡ Federico A. Gorelli,†,‡ Roberto Bini,‡,§ and Julien Haines∥
†
Istituto Nazionale di Ottica, CNR-INO, 50019 Sesto Fiorentino, Italy
‡
European Laboratory for Non Linear Spectroscopy (LENS), 50019 Sesto Fiorentino, Italy
§
Dipartimento di Chimica, Università degli Studi di Firenze, 50019 Sesto Fiorentino, Italy
∥
ICGM, CNRS, Univ. Montpellier, ENSCM, 34090 Montpellier, France

ABSTRACT: Molecular nitrogen is a benchmark system for condensed matter and, in

particular, for looking at universal properties of strongly confined dense systems. We
conducted Raman and X-ray diffraction measurements on a dense and disordered form of
molecular nitrogen subnanoconfined in a noncatalytic pure SiO2 zeolite under pressure, up to
50 GPa. In this form, N2−N2 interactions and, consequently, distances are found to be very
close to those of bulk N2 and intramolecular interactions progressively weaken upon
increasing pressure. Surprisingly, the filled zeolite is still crystalline at 50 GPa with silicon in
tetrahedral coordination by oxygen, which is a record pressure for this type of coordination
among all the known forms of silica. We have thus found a rationale for the polymerization of
a number molecules occurring in the microchannels of noncatalytic zeolites under pressure,
where the pressure threshold is found to be very similar to that observed in bulk samples.

T he high-pressure behavior of dense bulk nitrogen, which

we use as a reference here, has been one of the most
investigated among those of simple substances (see refs 1−13
and references therein). What triggered these studies was
nitrogen being a model system for a number of phenomena in
strongly condensed matter such as a rich variety of phase
transitions between thermodynamically stable and also
metastable phases, N2 orientational plastic disorder and
order−disorder transformations in solid state, and molecular
transformations in both solid and fluid states. The present high-
pressure phase diagram of solid nitrogen includes up to 12 to
13 distinct molecular phases in the 0−150 GPa pressure
range.9,12,6 Interestingly, pressure shifts of the crystalline
frequencies for the N2 stretching mode are strongly sublinear
and ultimately tend to level off or even exhibit maxima at
around 60−100 GPa. 1,3,5−10 This behavior signals the
progressive weakening of the N−N triple bond upon increasing
pressure, which, in turn, ends up in the formation of
nonmolecular, polymeric nitrogen above 100 GPa. Polymeric
nitrogen was indeed predicted by ab initio calculations14−23 and
also found experimentally.8−11,13,12
In this work we aimed to investigate the high-pressure
behavior of dense molecular nitrogen, confined on the
Ångstrom scale in the microchannels of a noncatalytic pure
siliceous zeolite. This type of confinement of dense guest
systems in a host scaffold obviously prevents the full
crystallization of the guests potentially ending up into highly
disordered subnanophases of these systems, and N2 certainly
represents a case system in this respect. The physical and
chemical behavior of matter in such exotic states is rather
unknown and intriguing and thereby worthy of investigation. In
particular, it is very important to characterize intermolecular
interactions for molecular systems in this state with a reduced
number of nearest neighbors and local dimensionality with
respect to the parent bulk system. The elucidation of this
fundamental aspect can provide a profound insight into
chemical reactions that may occur in strongly confined systems
in zeolites as the sole effect of pressure and confinement, which
we largely investigated in the recent past.24−27 Indeed, this
study is based on our large experience on noncatalytic purely
siliceous zeolites filled by molecular systems at high pressures.
We have first discovered that the insertion of simple molecules
such as Ar and CO2 in these zeolites, in amounts that
completely fill the pores, deactivates pressure-induced amorph-
ization (PIA) of the host scaffold at least up to 25 GPa.28,29
Then, we obtained purely pressure-induced self-assembly of
simple carbon-based molecules such as ethylene, acetylene, and
carbon monoxide within the zeolite channels, in the gigapascal
range, which led to the formation of novel nanocomposites
made of single-chain polymers embedded in the zeolite.24−27 X-
ray diffraction (XRD) measurements on the ambient pressure
recovered nanocomposites revealed that atoms forming the
embedded polymers are distributed around well-defined sites
with a large degree of disorder. We also found a similar type of
disorder in preliminary studies on dense atomic Ne confined in
zeolites under pressure. Interestingly, the threshold pressure for
confined polymerization was found to be very similar to the
polymerization threshold pressure in the same molecular
systems in bulk samples. Indeed, the present work provides a
rationale for this similarity. The zeolite we use in this work is
Received: April 13, 2017
Accepted: May 12, 2017
Published: May 12, 2017

© XXXX American Chemical Society 2406 DOI: 10.1021/acs.jpclett.7b00902

J. Phys. Chem. Lett. 2017, 8, 2406−2411
The Journal of Physical Chemistry Letters
silicalite-1, which is available as single crystals with sizes of tens
of micrometers and its pressure behavior up to ∼25 GPa is now
well known.28,30,31 Silicalite-1 is characterized by a framework
of 4-, 5-, 6-, and 10-membered rings of corner-sharing SiO4
tetrahedra forming interconnected, mutually orthogonal
straight and sinusoidal 5.5 Å diameter channels (refs 32 and
33 and references therein).
Here we show the high-pressure formation of a highly
disordered state or nanophase of dense molecular N2 confined
within the channels of silicalite-1 in the 0−50 GPa pressure
range, observed by means of in situ Raman spectroscopy in
diamond anvil cells (DACs). The pressure behavior of the N2
stretching frequencies of this disordered form provides physical
insight into the relevant microscopic interactions and
mechanisms. We also performed XRD measurements at the
maximum pressure and on the ambient pressure recovered
sample. These measurements serve as a monitor of the degree
of crystallinity of the host silicalite-1 and, as a consequence,
indirectly provide additional information on the confined
disordered nanophase of N2.
Dense nitrogen was loaded in DACs together with one to
two crystals of hydrophobic hydrogen-free silicalite-1-F with
their long axis corresponding to the crystallographic c direction
parallel to diamond culet surface. In these samples, nitrogen
was in two forms: confined N2 in silicalite-1 and bulk N2
surrounding the zeolite crystals. The gasket hole had an initial
diameter and a thickness of about 100 and 40 μm, respectively.
Silicalite-1 crystals have sizes of 80 × 40 × 40 μm3, and they
were broken into several strongly oriented pieces after the
loading pressure was applied and the sample chamber thickness
and diameter were consequently reduced. Two types of Raman
spectra were observed in these samples for points in pure bulk
N2 and points in the silicalite-1 crystals, respectively. It was then
clear that silicalite-1 was almost bridging the diamond anvils,
except thin micron size layers of bulk nitrogen on the top and
the bottom. In Figure 1, we report a selection of Raman spectra
of the N2/silicalite-1 mixture, measured at the top of silicalite
crystals upon increasing pressure up to ∼50 GPa in the
frequency range of the N2 stretching. Here we observe several
peaks for confined nitrogen, whose number, linewidth, and
total spread increase upon increasing pressure, and also the
frequencies exhibit positive pressure shifts. At the lowest
pressure, 0.7 GPa, confined nitrogen exhibits three sharp peaks
spaced by 1.2 to 1.6 cm−1. These can be reasonably assigned to
N2 molecules in three different local environments: sites along
the straight channels, along the zigzag channels, and at the
intersection of the two types of channels. At least two
observations support that this fine Raman structure is not
specific to N2 but rather to the structure of the channels. First,
we performed some measurements on O2/silicalite-1 mixtures,
where at similar pressures confined oxygen also exhibited three
finely spaced Raman peaks for the O2 stretching (Figure 1,
inset). Then, preliminary Raman measurements on N2/TON
and O2/TON mixtures at these pressures, where TON is a pure
SiO2 zeolite with a 1D channel system with a single type of
channels, show that confined N2 and O2 exhibited only a single
peak instead of three. It is then highly probable that confined
N2 molecules in silicalite-1 distribute on the three different
types of site with some degree of disorder already at pressures
of tenths of gigapascals, based on our experience of the
polymer/zeolite composites.24−27 At 13.6 GPa we observe at
least four poorly resolved peaks for confined N2 (see arrows in
Figure 1), which split each other by 5−12 cm−1. The total
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Figure 1. Selected Raman spectra of a N2/silicalite-1 sample measured
upon increasing pressure. Vertical sticks: peaks of bulk solid N2 phases,
indicated by Greek letters (f is the fluid phase). Arrows: peaks for
confined N2 at 13.6 GPa. Inset: Raman spectrum of an O2/silicalite-1
sample at 0.6 GPa; vertical stick: peak of bulk fluid O2. The spectra
have been normalized to the same peak intensity; then, they have been
vertically shifted.
spread of these components and their individual linewidths are
larger than those observed at 0.7 GPa by about one order of
magnitude. While the increased total frequency spread is
related to increased microscopic interactions in a sense that will
be specified below, the increased number of peaks testifies for
confined N2 being distributed among a larger number of
average sites within the channels. Also, the strongly increased
linewidth of the single peaks suggests that the molecules are
distributed around the average sites with a significantly
increased degree of disorder. Above 15−20 GPa the peaks
merge into a single, broad, and featureless band, strongly
suggesting that the distribution of molecules within the
channels is now entirely statistical, and hence the disorder of
confined N2 is increased further in these conditions. It is then
reasonable to think that the broad, single band roughly
resembles the density of intramolecular N−N stretching states,
DOS, of this highly disordered form, as it was an amorphous
material. The total width of this band increases up to the
maximum investigated pressure, 50 GPa, and then reversely
decreases upon reducing pressure; nevertheless, the fine
structure observed in the upstroke run is never recovered.
In Figure 2, we report the XRD pattern of the N2/silicalite-1
mixture measured at the maximum pressure of 50.3 GPa, where
we observe two distinct Bragg reflections of silicalite-1 at low
diffraction angles of 4.059 and 4.760°, respectively. These
reflections are single crystal-like, meaning that the silicalite-1
chips are strongly oriented. The crystals are highly strained. We
also see a very weak peak of silicalite-1 between 12.0 and 12.5°.
The whole pattern is superimposed to an intense and broad
background signal due to Compton scattering from diamonds
DOI: 10.1021/acs.jpclett.7b00902
J. Phys. Chem. Lett. 2017, 8, 2406−2411
The Journal of Physical Chemistry Letters
Figure 2. XRD pattern of a N2/silicalite sample at 50.3 GPa and of the
ambient pressure-recovered sample. Insets: selected portion of the 2D
XRD patterns. The white large central area is the shadow of the beam
stop glued on a tungsten wire (vertical white narrow strip), and the
black spots at the edge of this area, which have been masked before
performing the 2D average, are due to double diffraction in the
diamond anvils with two scattering events. The very weak peak at 12.0
to 12.5° at 50.3 GPa is also due to silicalite-1, whereas the broad,
diffuse peak at ∼11.5° in the recovered sample is due to amorphous
silica.
and air. Remarkably, we do not detect diffuse scattering from
potential amorphous silica, which indicates that the majority of
our silica sample is still crystalline silicalite-1, although we
cannot exclude that a minor portion of silica is indeed
amorphous with an XRD signal that is overwhelmed by the
strong Compton background. PIA of silicalite-1 in non-
penetrating, pressure-transmitting media has been found to
occur at several gigapascals, whereas the insertion of dense
simple molecular systems deactivates PIA at least up to 25
GPa.28 Here we found that the insertion of dense N 2
deactivates PIA up to at least 50 GPa, which is a record
pressure in this respect and it is also a record pressure for
silicon being four-fold-coordinated by oxygen in any known
form of silica. Very importantly here, our findings show that a
guest highly disordered dense N2 form is hosted in a porous
crystalline, although highly strained, scaffold. The increased
disorder of confined nitrogen at high pressures is then likely to
originate, at least partially, from the strain of the host system. It
is also important to note that the deactivation of PIA in
silicalite-1 is a strong piece of evidence that N2 completely fills
the zeolite and, as a consequence, that confined highly
disordered nitrogen is a true nanophase or -state as a whole
rather than being a trivial ensemble of isolated impurities. The
XRD pattern of the recovered sample at ambient pressure still
confined by the gasket after it has been removed from the DAC
is also shown in Figure 2. Nitrogen completely flowed out of
the sample chamber under these conditions, and the sample is
pure silica. In this pattern, we observe two weak and spotty
peaks at 3.01 and 3.29° from a highly oriented and strained
phase obtained from silicalite-1 and a broad, diffuse peak at
∼11.5°, that is, the first sharp diffraction peak of amorphous
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silica. Silicalite-1 thus partially amorphized upon reducing
pressure, which may be due either to loss of confined N2 from
the zeolite or to the silicalite-1 being damaged by inserted N2
expanding to a larger extent than the host scaffold. The partial
amorphization of silicalite-1 reasonably explains the observation
that the fine structure of the N2 stretching Raman peak for
confined nitrogen was not recovered upon reducing pressure.
To provide a quantitative description of microscopic
interactions probed by the N2 molecules in the confined
state, we have calculated the spectral moments of the N2
stretching Raman band as a whole, which allowed us to describe
essential aspects of these interactions not depending on the fine
structure details. The moments have been calculated from the
measured spectra after subtraction of the smooth diamond
fluorescence background and of the sharp peaks of bulk
nitrogen, which, in turn, involved a fitting procedure. In Figure
3 we report the pressure shift of the spectral centroid, that is, of
Figure 3. Pressure shift of the frequency centroid of the Raman N2
stretching peak for confined nitrogen. Full and open circles and black,
thick line: data points measured upon increasing and decreasing
pressure, respectively, and a guide for the eye fitted through the points.
Error bars originate from the peak fitting procedure and spatial
variation of frequencies and pressures. Red1 and green3 lines:
reproduced literature data for the N2 stretching frequencies of bulk
crystalline N2, ν1, and ν2.
the average wavenumber vavg calculated as vavg = ∫ vI(v)dv/
∫ I(v)dv, where v and I(v) are the wavenumber and the spectral
intensity, respectively, together with the literature crystalline
frequency components of bulk N2.1,3 Pressure behavior of the
spectral centroid of confined disordered N2 compares very well
with those of the ν2 manifold of bulk N2. In particular, this
behavior for the confined form is markedly sublinear similar to
the crystalline frequencies. These findings have one very
important implication: the pressure dependence of microscopic
interactions probed by N2 molecules in the confined form is
dominated by that of the intermolecular N2−N2 interactions
between nearest N2 neighbors, which are very similar, along
with intermolecular distances to those in the molecular crystal
at the same pressures. Specifically, the sublinear character of the
frequency pressure shift of confined disordered nitrogen
DOI: 10.1021/acs.jpclett.7b00902
J. Phys. Chem. Lett. 2017, 8, 2406−2411
The Journal of Physical Chemistry Letters
suggests that in parallel with bulk N2 a progressive weakening
of the N−N triple bond occurs in this form upon increasing
pressure, which may end up in some form of polymeric,
confined nitrogen at sufficiently high pressures. Interestingly,
the result is that the interactions between N2 and the silicalite-1
pore walls, that is, N−O interactions, although strong in
principle, may only weakly affect the pressure dependence of
microscopic interactions experienced by N2. This point
indicates that N2−N2 distances and molecular packing along
the channels of the zeolite, that is, along the stacking directions
of confined molecules, are more easily changed upon increasing
pressure than the N−O distances, an argument that calls for
future structural studies now beyond the scope of the work.
Furthermore, the spectral centroid of confined N2 being very
close to the ν2 rather than the ν1 frequency of bulk N2 suggests
that a particular type of orientational disorder for confined
nitrogen occurs. Because ν2 and ν1 are the stretching
frequencies for disk-like and sphere-like orientationally
disordered molecules in solid N2, respectively, our result
suggests that disk-like orientational disorder prevails in
confined disordered nitrogen.
Confirmation of the scenario given above for microscopic
interactions and additional information on these forces are then
obtained from the calculation of the spectral standard deviation
σ, as σ2 = ∫ (v − vavg)2I(v)dv/∫ I(v)dv. Indeed, 2σ is a
reasonable measure of the total frequency spread of the N2
stretching DOS for disordered N2, and we can compare this
quantity to the total spread observed in bulk N2 crystalline
phases. Although for crystalline bulk N2 Raman peaks only
sample the Brillouin zone center, the total spread of DOS in
this case can be reasonably estimated as the total splitting
between the different crystalline frequency components, that is,
as the difference between ν1 and the lowest ν2 component,
which we obtained from literature.1,3 In Figure 4, we compare
the total spread of the N2 stretching DOS for confined
disordered N2 and for crystalline bulk N2, respectively, as a
function of pressure. It is very striking how consistent these two
behaviors are with each other. This result is a strong
confirmation of pressure dependence of microscopic inter-
actions seen by N2 in the confined form being dominated by
pressure dependence of nearest-neighbor intermolecular
interactions. These interactions, together with intermolecular
distances, are very close to those in the molecular crystal, and
they are the main origin of the total spread in the Raman peaks
of confined disordered N2. Also, the similarity of N2−N2
interactions and distances between confined nitrogen in
silicalite-1 and the bulk crystal clearly show once again, in
addition to PIA being deactivated up to at least 50 GPa, that
confined nitrogen is a dense state of closely stacked molecules,
which are indeed very far from being isolated guest impurities
in the host scaffold.
In conclusion, we have shown that high-pressure confine-
ment of N2 on the Ångstrom scale in a purely siliceous zeolite,
at tens of gigapascals, leads to a highly disordered dense form of
molecular N2. On the contrary, the zeolite remains mostly
crystalline up to 50 GPa, although the crystal is highly strained;
this pressure is certainly a record pressure for silicon being four-
fold coordinated in any known form of silica. The pressure
dependence of microscopic interactions affecting N2 in this
form is dominated by that of the N2−N2 intermolecular, van-
der-Waals-type interactions, which are very similar, along with
intermolecular distances, to those in bulk, crystalline N2. From
these findings, we can straightforwardly provide important clues
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Letter
Figure 4. Pressure shift of 2σ, where σ is the frequency standard
deviation with respect to the frequency centroid of the Raman N2
stretching band for confined nitrogen. Full and open circles and black,
thick line: data points measured upon increasing and decreasing
pressure, respectively, and a linear guide for the eye fitted through the
points. Error bars originate from the peak fitting procedure and spatial
variation of frequencies and pressures. Red1 and green3 lines:
reproduced literature data for the difference between the maximum
and the minimum N2 stretching frequencies of bulk, crystalline N2.
on high-pressure polymerization reactions that we observed in
confined simple C-based molecular systems in purely siliceous
zeolites.24−27 In these systems, we observed polymerization at
pressures very close to those observed in bulk samples. This is
now clearly understandable in terms of intermolecular
interactions and, consequently, distances being very similar in
the confined and in the bulk systems. This general result leads
to foresee the pressure threshold for any other possible
chemical reactions that may occur between molecules confined
in noncatalytic zeolites once this threshold is known for the
bulk system. In particular, on N2/siliceous zeolite systems there
is a very intriguing perspective. Similarly to bulk N2, confined
disordered N2 may transform into polymeric nitrogen forms
above 1 Mbar because N2−N2 intermolecular interactions are
similar in the two systems. These confined polymeric forms
should be made of single chains of N atoms fitting the channels
of the zeolite and would thereby differ from the known, 3D
polymeric forms of bulk nitrogen.
■ METHODS
High-purity nitrogen was cryoloaded in DACs at 77 K together
with commercially available hydrophobic hydrogen-free silica-
lite-1-F (SOMEZ, France). DACs were equipped with 300 μm
culet and ultralow fluorescence Ia diamonds, and we used Re as
the gasket material. Pressure was measured by the ruby
fluorescence technique.34 Raman spectra were performed using
the 647.1 nm line of a Kr+ laser as the excitation source.
Backscattering geometry was used with X20 Mitutoyo micro-
objective giving a laser spot of <3 μm, and the sample signal
was detected with an Acton/SpectraPro 2500i single mono-
chromator with a total resolution, including laser linewidth, of
∼0.6 cm−1, equipped with holographic super notch filters and a
CCD detector (Princeton Instruments Spec-10:100 BR).35
Meshes of typically 3 × 3 equally spaced points with 20−30 μm
DOI: 10.1021/acs.jpclett.7b00902
J. Phys. Chem. Lett. 2017, 8, 2406−2411
The Journal of Physical Chemistry Letters
spacing were measured for each pressure with an integration
time of 300−600 s per point. Angle-dispersive, powder XRD
patterns were obtained using a Mo microsource (λ = 0.71073
Å), equipped with multilayered focusing mirrors (Xenocs-
GeniX Mo Small Spot). The final X-ray spot on the sample and
beam divergence were 50 μm and 0.2°, respectively. The
diffracted signal was detected by a CCD detector (PI-SCX
4300). The typical integration time for each pattern was 4 h.
The diffraction patterns were analyzed and integrated using the
DIOPTAS program.36
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: santoro@lens.unifi.it.
ORCID
Mario Santoro: 0000-0001-5693-4636
Roberto Bini: 0000-0002-6746-696X
Julien Haines: 0000-0002-7030-3213
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We acknowledge the PRIN project ZAPPING, number
2015HK93L7, granted by the Italian Ministry of Education,
Universities and Research, MIUR. We are also grateful for the
support from PICS bilateral project CNR/CNRS (Italy/
France), 2014-2016: Multifunctional zeolite/polymer nano-
composites. We also thank the Deep Carbon Observatory
(DCO) initiative under the project Physics and Chemistry of
Carbon at Extreme Conditions and the Ente Cassa di
Risparmio di Firenze under the project Firenze Hydrolab 2.
■
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